Acid anthraquinone dyestuffs



United States Patent ACID ANTHRAQUINONE DYESTUFFS Peter Hindermann,Batterie, Basel, Peter Trautzl, Basel, and Jean-Pierre Jung, Riehen,near Basel, Switzerland, assignors to J. R. Geigy A. G., Basel,Switzerland, a Swiss firm N0 Drawing. Application December 23, 1955Serial No. 554,917

Claims priority, application Switzerland December 31, 1954 8 Claims. Cl.260-373) The present invention concerns reddish blue acid anthraquinonedyestufis which are suitable for the dyeing of natural and syntheticpolypeptide fibres. Due to their high aifinity, they are particularlysuitable for the dyeing of wool from a neutral to weakly acid bath. 'Italso concerns processes for the production of the new acid wooldyestuffs. Further, it concerns dyeing processes for natural andsynthetic polypeptide fibres using the new anthraquinone dyestufi's aswell as, as industrial product, the pcgpeptide material fast dyed withthe aid of these dyest s.

It has been found that very valuable acid anthraquinone dyestuffs whichdye wool very fast in reddishblue shades even from a neutral to weaklyacid bath are obtained if anthraquinone derivatives having" substituentsWhlCh can be exchanged in the 1.4-position and which may also possiblybe further substituted are reacted by methods known per se at a raisedtemperature with 6-alkyl-l-aminobenzene aryl ethers substituted in the2-posit1on of the amine substituted benzene ring by an alkyl or ethergroup, the amine containing benzene ring of which may possibly alsocontain further alkyl substituents, to form the corresponding1.4-bis-phenylamino compounds, sulphonating these dye bases andconverting the dyestufI' sulphonic acids into the water soluble salts.

Examples of anthraquinone derivatives having substituents which can beexchanged in the land 4-positions of the anthraquinone ring which areusable according to the present invention are e. g. the 1.4-dihalogen,the 1- halogen-4-nitro, the l-halogen-4-hydroxy, the l-alkoxy-4-halogen, the 1-hydroxy-4-nitro and, in particular, also the1.4-dihydroxy anthraquinones. These anthraquinone derivatives can bestill further substituted, preferably by non-ionogenic substituents, forexample in the 6- and/or 7-position of the anthraquinone ring forexample by fluorine, chlorine, bromine, arylthio and alkyl .sulphonylgroups. 1.4-dichloro and, in particular dibromo anthraquinones as wellas the 1.4-dihydroxy anthraquinones are particularly suitable, all ofwhich can be further substituted as indicated.

The generic expressions ether group and aryl ether group are intended toembrace oxygen others as well as thio ethers in the definition of thepresent invention. In the '6-alkyl-1-aminobenzene aryl ethers whichcontain either an ether or an alkyl group in the 2-position of theamine-containing benzene ring, the alkyl substituents are advantageouslymethyl groups. Also, possibly higher alkyl groups, for example the ethylgroup, the isopropyl group or hydrogenated rings linked in that positionto the benzene ring can form the alkyl substituents. Advantageously, thearyl radical of the aryl ether group is a phenyl radical which can befurther substituted non-ionogenically as desired, for example byhalogen, alkyl,

aralkyl, aryl, alkyl and aryl ether, alkyl and aryl sulphonyl, aliphaticor. aromatic keto groups, or also a See 2 naphthyl radical, which latteralso can be further substituted nonionogenically as desired. The6-alkyl-1- aminobenzene aryl ethers used according to the presentinvention are new. They are obtained from the corresponding6-alkyl-1-nitro-halogen benzene compounds by reacting with alkali metalphenolates, alkali metal naphtholates, alkali metal thiophenolates,alkalimetal thio.- n'aphtholates, advantageously in the presence. of anexcess of hydroxyl compound or the sulphohydr'yl compound used, byheating to a fairly high temperature and then reducing the nitro groupto the amino group. The -6-alkyl-l-nitro-halogen benzene compounds usedas starting materials are obtained from the corresponding6-alkyl-l-amin'o-Z- or -4-halogen benzenes by diazotising and replacingthe diazo group by the nitro group in the presence of potassium-cobaltnitrite by the. usual methods. Thus, for example,6-methy1-1-nitro-2-chlorobenzene and4.6-dimethyl-l-nitro-Z-chlorobenzene as well as 2.6-dimethyl-l-nitro-3-or -4-bromobenzene can be used which produce particularly valuable6-alkyl-1-aminobenzene aryl ethers usable according to the presentinvention, for example, the 1-amino2.6-dimethyl-4-phenoxy-,-4-phenylthio-, -4-(2- or 3'- or 4-methylphenoxy)-,-'4-(4'-methylphenylthio)-, -4-(4'-chlorophenylthio)-, -4-(2'- or 3'- or4'-chlorophenoxy)-, -4(4'-tert. butylphenoxy) '-4-(4 tert. amylphen0xy)--4 (4 benzylphenoxy)-, 4 (4 phenylphenoxy)-, -4-(4'-phenoxyphenoxy)-,-4-(4'-btuylor -phenyl-sulphonylphenoxy)-, -4-(4acetylor-benzoyl-phenoxy)-benzene, as well as the corresponding 2.6-dimethyl-l-aminobenzene-3-aryl ethers, G-methyl-l-aminobenzene-Z-arylethers and 4.6-dimethyl-1-aminobe1rzene-Z-aryl ethers, also the6-methyland the 4.6-dimethyl-1-amino-2(1'- or -2-naphthyloxy)-benzenesand the 2.6-dimethyl-l-amino-4-(1'- or -2' naphthyloxy)-benzenes.

The condensation with the anthraquinone derivatives having movablesubstituents in the land 4-positions is performed by methods known perse, for example, .by heating the components as a melt or in the presenceof low fatty acids, higher boiling alcohols such as butanol or ethyleneglycol monomethyl or mon'oethyl ether. It can also be performed possiblyin the presence of agents which bind the mineral acid or which reducethe quinone to some extent as Well as in the presence of coppercontaining catalysts or stabilisers containing boron. It Iis alsopossible to perform the condensation in steps by first replacing onlyone of the substituents which can be exchanged and then the other byaryloxy or arylthio-6- alkyl-l-phenylamide radicals.

The dye bases, which are possibly purified by recrystallisation, bywhich the 1.4-bis-(aryloxyor arylthig-alkylphenylamino)-anthraquinoneswhich, asstated above can be further substituted nonionogenically, are.to be understood, are finally sulphonated by methods which are alsoknown per se. In the sulphonation process care should be taken that,generally, not more than twosulphon'ic acid groups are introduced if anoptimal drawing power onto wool from a neutralto weakly acid bath flSdesired. The sulphonation can be performed with concentrated sulphuricacid, with oleum, with chlorosulphonic acid, with sulphuric acidtrioxide advantageously in the form of the addition product withpyridine or dioxan, possibly in inert solvents for the dye bases.Fin'ally, the dyestulf sulphonic acids freed from accompanyingsubstances are converted in aqueous suspension into the water solublealkali'or ammonium salts, e. g. into the lithium, sodium, potassium orammonium salts. These alkali salts dissolve in both hot water and inconcentrated sulphuric acid with a blue colour. They dye wool in aneutral to weakly acid bath in valuable reddish blue shades. The wooldyein gs have very good wet and light fastness properties. The dyestuflscan also be a blue colour.

' reflux for several hours.

used for the dyeing of other natural and synthetic polypeptide fibres,e. g. for the dyeing of silk, lanital fibres, super-polyamide andsuperpolyurethane fibres. H The following examples give more exactinformation regarding the production and use of the new acidanthraquinone dyestutfs. They serve, however, only to .furtherillustrate the invention without limiting it in any way. Where nototherwise stated, parts are given as parts by weight and thetemperatures are in degrees centigrade.

Where parts by volume are expressly mentioned, their relationship toparts by Weight is as that of litres to kilogrammes.

. Example 1 A mixture of 15 parts of quinizarin, 9.1 parts of leuco as athick, crystalline mass. Some of it is in the leuco form. 200 parts ofN-butyl alcohol, 4.2 parts of 30% caustic soda lye and 5 parts of sodiumperborate are added at 80 to convert the product into the dye base andthe reaction mixture is boiled for some hours under It isanilido)-anthraquinone of the formula:

is drawn ofl under suction, washed with about 70 warm N-butyl alcoholand the amine adhering thereto is removed with warm, strongly dilutedhydrochloric acid.

The dried dye base is then sulphonated by methods known per se, forexample by stirring parts in 100 parts of concentrated sulphuric acid at25 until a sample dissolves completely in a lot of hot Water. Thedyestuff is precipitated by diluting with water, drawn oil under suctionand converted into the sodium salt in the usual way,

' isolated and dried. It is a dark blue powder which dissolves in waterand in concentrated sulphuric acid with It dyes wool, silk and polyamidefibres from a neutral bath in very fast reddish blue shades.

The same dyestulf is attained if instead of the mixture of 15 parts ofquinizarin and 9.1 parts of leuco quinizarin, a mixture of 15 parts of1-amino-4-hydroxyanthraquinone and 9.1 parts of the corresponding leucocompound is used.

Similar dyestufis are obtained if in the above example, instead of4-amin0-3.S-dimethyl-l-phenoxybenzene, 105.2 parts of4-amino-3.5-dimethyl-l-(lor -2-naphthyloxy)- benzene are used andotherwise the same procedure is followed.

Example 2 100 parts of 4-amino-3.4'.5-trimethyldiphenyl oxygen ether arestirred at 170-180 with 27.7 parts of 1.4-dichloranthraquinone, parts ofpotassium acetate, 0.1 part of copper powder and 0.1 part of copperacetate for 10 hours. The melt is then cooled to 60, 300 parts of methylalcohol are added and the whole is boiled under The crystallinecondensation product, which is obtained in good yield, is filtered oil?and washed with warm methanol, strongly diluted hydrochloric acid andwarm water. By recrystallising once CH3 is obtained in fine blue-black,bronze-gleaming little needles. To sulphonate, the dye base is stirredin 5 to 10 times the amount of concentrated sulphuric acid at 20' 25until a sample dissolves completely in water. The product is stirred inice water, the precipitated dye acid is filtered ofi under suction,again pasted in water, converted into the neutral sodium salt withcaustic soda lye and isolated without salt at room temperature. Whendry, the dyestuff is a dark blue powder which dissolves in water and inconcentrated sulphuric acid with a blue colour. It dyes wool, syntheticpolyamide fibres, charged and uncharged silk in reddish blue shadeswhich are wet and light fast.

The same dyestufi is obtained also if, in the above example, 28.75 partsof 1-chloro-4-nitroanthraquinone or 27.25 parts of1-methoxy-4-chloranthraquinone are used instead of 27.7 parts of1.4-dichloranthraquinone.

Similar dyestufis are obtained if, in the above example, instead of theaminodiphenyl ether used, 130 parts of4-amino-3.5-dimethyl-1-(4-benzylphenoxy)-benzene or the same number ofparts of 4-amino-3.5-dimethyl-l-(4'- phenoxyphenoxy)-benzene are usedand otherwise the same procedure is followed.

Also the condensation can be performed as described in Example 1 with amixture of quinizarin and .leueo quinizarin in the melt in the presenceof boric acid.

Example 3 120 parts of 4-amino-3.5-dimethyl-4'-ch1orodiphenyl oxygenether, 24 parts of quinizarin, 30 parts of amyl alcohol and 8 parts of30% hydrochloric acid are stirred at -95 during which process 2 parts ofzinc dust are added in small portions within 20-30 minutes. After adding5 parts of boric acid, the reaction mass is kept for 24 hours at -115 Afurther 200 parts of N-amyl alcohol are then added and the whole isstirred for another hour at 60. The condensation product which hasprecipitated in crystalline form is filtered off, washed with warmmethyl alcohol, strongly diluted mineral acid and then with water. Anexcellent yield ofl.4-bis-(2'.6'-dimethyl-4-p-chlorophenoxyanilido)-anthraquinone of theformula:

precipitates out. After drying, the base is added to 10 times the amountof concentrated sulphuric acid. The sulphonation mass is stirred at 2030until a sample dissolves completely in water. The dyestufi is isolatedin the usual way and converted into the sodium salt. It is a dark bluepowder which dissolves in water and in sulphuric acid cone. with a bluecolour. It dyes wool, silk and polyamide fibres in very fast reddishblue shades and .erties.

Example 4 parts of quinizarin, 9.1 parts of leuco quinizarin, 97.2partsof 4-amino-3.4'.5-trimethyl diphenyl sulphide,

9 parts of metaboric. acid are melted with parts of glacial acetic acidand 3.5 parts of hydrochloric acid in a nitrogen atmosphere and the meltis kept for hours at 1l0-ll5. During this time, the condensation productgradually precipitates in crystalline form. 200 parts of N-butylalcohol, 5 parts of a 30% caustic soda lye and 5 parts of sodiumperborate are added and the whole is boiled for some hours under refluxuntil the leuco compound is oxidised to the normal dye base. It is thenallowed to cool to room temperature, the crystalline 1 .4-bis-2'.6'-dimethyl-4-p-tolylmercaptoanilido anthraquinone of the formula:

is drawn off under suction and washed first with about 70 warm N-butylalcohol and then with warm, strongly diluted hydrochloric acid andfinally-with water. The dye base is then dried.

10 parts of the condensation product are stirred at 20-25" in 10 timesthe amount of concentrated sulphuric acid until a sample completelydissolves in a lot of hot water. The dyestuff is precipitated by pouringinto ice water, the precipitate is filtered oflf, the filter cakes aredissolved in 500 parts of water, neutralised with sodium carbonate andthe dyestufl is isolated as the sodium salt. It is a dark powder whichdissolves in water and in concentrated sulphuric acid with a bluecolour. The dyestutf has very good drawing power from a neutral bath. Itdyes wool, synthetic polyamide fibres and silk in very fast blue shades.

If in the above example, 91.6 parts of 4-amino-3.5-dimethyldiphenylsulphide or 102.8 parts of 4-amino- 3.3'.4.5-tetramethyldiphenylsulphide or 114 parts of 4- amino-3.5-dimethyl-4-n-butyldiphenylsulphide are used instead of 97.2 parts of 4-amino-3.4'.5-trimethyldiphenyl F sulphide, then similar blue dyestuffs which draw Well from aneutral dyebath are obtained, the Wool dyeings of which have goodWashing, milling and light fastness prop- Example 5 Y 15 parts ofquinizarin, 9.1 parts of leuco quinizarin,

' 105.4 parts of 4-amino-3.5-dimethyl-4-chlorodiphenyl sulphide and 9parts of metaboric acid are condensed in the presence of glacial aceticacid and hydrochloric acid Nfbutyl alcohol. in the presence of sodiumperborate to,

form1.4-bis-(2.6'-dimethyl-4'-p-ch1orophenylmercaptoanilido)-anthraquinoneofthe'formula I t IFHO O CH3 v cm i The dye base is obtained in finedark, bronze-gleaming little needles by crystallisation from N-butylalcohol. The dyestufi is sulphonated also as described in Example 4 andisolated in the form of the sodium salt. It is a dark powder whichdissolves in water and in concentrated sulphuric acid with a blue.colour. Blue dyeings are obtained on wool, silk and polyamide fibres ina neutral bath which are very fast to milling.

If the 105.4 parts of 4-amino-3.5-dimethyl-4-chlorodiphenyl sulphide arereplaced by 124 parts of 4-amino-3.5-

dimethyl-4-bromodiphenyl sulphide or by 119.2 parts of4-amino-3.5-dimethyl-3'.4'-dichlorodiphenyl sulphide, then dyestufis areobtained which dye wool and silk in similar fast blue shades.

Example 6 18 parts of 6-chloroquinizarin, 9.45 parts of leuco-6-chloroquinizarin, parts of 4-amino-3.2'.5-trimethyldiphenyl oxygenether, 9 parts of metaboric acid are condensed in a nitrogen atmospherein 25 parts of N-amyl alcohol for 30 hours at -125. The condensationproduct obtained is boiled under reflux for several hours whileintroducing air in order to convert the part of the condensation productwhich is in the leuco form into the anthraquinone of the formula:

The crystalline precipitate is then drawn olf hot under suction andrecrystallised once from nitrobenzene. The crystalline, bronze-gleamingdye base obtained is sulphonated in 5 to 10 times the amount ofconcentrated sulphuric acid at 15-25 until a sample completely dissolves in a lot of hot water. The dye base is then poured into ice waterand the dyestufi is isolated in the usual way as sodium salt and dried.It is a dark powder which dissolves in water and in concentratedsulphuric acid with a blue colour. It dyes wool, silk, and polyamidefibres from a neutralbath in blue shades which are fast to light andmilling.

If insteadof the mixture of 18 parts of 6-chloroquinizarin and 9.45parts of leuco-6-chloroquinizarin, a mixture of 20 parts of 6-bromoquinizarin and 11.9 parts of leuco-6-bromoquinizarin or a mixtureof 17 parts of 6- fluoroquinizarin and 8.8 parts ofleuco-6-fluoroquinizarin is used, then similar blue dyestuffs which drawwell from a neutral bath and are fast to milling are obtained.

Exanilple 7 A mixture made up from 20 parts of 6.7-dichloroquinizarinand 11 parts of leuco-6.7-dichloroquiniza1'in, 9

- parts of metaboric acid and 100 parts of 4-amino-3.3'.5-

trimethyldiphenyl oxygen ether is melted with 25 parts of glacial aceticacid and 3.5 parts of 30% hydrochloric the formula:

l CH3 lHz CH 6 -Q Q CH3 (ilH;

obtained in crystalline form is drawn ofl. hot under suction, washedwith warm ethyl alcohol, hot diluted hydrochloric acid and then withwarm water and dried. The dye base in the form of a bronzy dark crystalpowder is obtained by crystallisation from nitrobenz'ene. To sulphonate,the dye base is stirred at 15 30 in 10 times the amount of concentratedsulphuric acid until a sample is completely soluble in a lot of hotwater. It is then pasted into ice water, the precipitated dye acid isdrawn off under suction, again pasted in water and con- .verted into theneutral sodium salt of the dyestufi with sodium carbonate. The sodiumsalt is isolated at room temperature without the addition of salt. It isa dark blue powder which dissolves in water and in concentratedsulphuric acid with a blue colour and dyes wool, charged .or unchargedsilk in reddish-blue shades which are fast to wet and light.

If instead of 100 parts of 4-amino-3.3.5-trimethyldiphenyl ether, 106parts of 4-amino-3.3.5.5-tetramethyldiphenyl ether, 118 parts of4-amino-3.5-dimethyl-4'-isopropyldiphenyl ether or 113 parts of4-amino-3.5-dimethyl-4-methoxydiphenyl ether are condensed, thendyestuifs which dye wool from a neutral bath in blue shades ofcorresponding wet and light fastness are obtained.

Example 8 A mixture of 12 parts of 1.4-dihydroxy anthraquinone, 12.1parts of leuco quinizarin, 9 parts of metaboric acid and 79.6 parts ofS-methyl-Z-amino-l-phenoxybenzene is melted with 25 parts of glacialacetic acid and 3.5 parts of 30% hydrochloric acid and the thin liquidmelt is kept for 30 hours at 110-115 in a carbonic acid atmosphere.After this time, the condensation product has precipitated as a thickcrystalline mass. Some of it is in the leuco form. To convert into thedye base, 200 parts of N-butyl alcohol and 4.2 parts of 30% caustic sodalye are added at 90 and air is introduced through the reaction mixtureat 90100 for some hours until the leuco compound has disappeared. It isallowed to cool to room temperature and the crystalline, bronzy1.4-bis-(2'-phenoxy6-methylanilido)-anthraquinone of the formula:

0 G H I 8 is drawn off under suction. After washing the filter reiduewith hot methyl alcohol, the dyestufl base is-obtained in a pure form.The dried dye base is then sulphonated by the usual methods, for exampleby stirring 10 parts in'lOO parts of concentrated sulphuric acid at 1520until a sample dissolves completely in a lot of hot water. The dyestuffis precipitated by dilution with water, drawn off under suction andconverted in the usual way into the sodium salt, isolated and dried. Itis a dark 'blue powder which dissolves in water and in concentratedsulphuric acid with a blue colour and dyes wool, silk and polyamidefibres from a neutral bath in the presence of ammonium sulphate in veryfast reddish blue shades.

If instead of 79.6 parts of 3-methyl-2-amino-l-phenoxybenzene, 85.2parts of 2-amino-3.2- or -3.3'- or -3.4'-dimethyldiphenyl oxygen etheror 93.4 parts of 3-methyl- 2-amino-4-chloro-l-phenoxybenzene or 91.6parts of 3- methyl-2-amino-1-(4'-methoxyphenoxy)-benzene or 115.6 partsof 3-methyl-2-amino-1-(4-benzylphenoxy)-benzene or 116.4 parts of3-methyl-2-amino-1-(4-phenoxyphenoxy)-benzene or 121.2 parts of3-methyl-2-amino-l-(4- benzoylphenoxy)-benzene or 99.6 parts of3-methyl-2- amino-1-(1'- or -2-naphthoxy)-benzene are condensed, thensimilar dyestuffs which draw well from a neutral bath are obtained.

Example 9 12 parts of 33% hydrochloric acid are added at 90 to a melt of24 parts of 1.4-dihydroxy anthraquinone, 90.8 parts of2-amino-3.4'.5-trimethyl-1-phenoxybenzene and 25 parts of glacial aceticacid and then 3.3 parts of zinc dust are added in small even portionswithin 10 minutes. Then 9 parts of metaboric acid are added and the thinliquid melt is kept for 24 hours at 110-115 After this time, thecondensation product has precipitated as a thick, crystalline mass. Toconvert the part of the dye base which is in the leuco form, 200 partsof sec. butyl alcohol and 10 parts of 30% caustic soda lye are added atand air is introduced into the reaction mixture for some hours at 85-90"until the leuco compound has disappeared. It is cooled to roomtemperature and the crystalline, bronze-gleaming 1.4-bis-anilidoanthraquinone of the formula:

ll i

is drawn off under suction. It is washed with hot sec. butyl alcohol,strongly diluted mineral acid and water and dried. The dye base isobtained in good yield and purity.

10 parts of this condensation product are added to parts of sulphuricacid and the whole is stirred at l530 until a sample dissolvescompletely in water. The sulphonation mass is then stirred into amixture of ice and water, the precipitate is filtered ofi, the filtercakes are dissolved in 500 parts of water, neutralised with sodiumcarbonate and the dyestufl is isolated as sodium salt with sodiumchloride. It is a dark powder which dissolves in water and inconcentrated sulphuric acid with a blue colour. The dyestufr dyes wooland silk from a neu tral bath in blue shades which have good fastness tomilling, sea water and light.

If instead of the 90.8 parts of 2-amino-3.4'.5-trimethyl-'l-phenoxybenzene, 964 parts of 2-amino-3.3'.5.5'-tetra- 9methyl-l-phenoxybenzene or 115.6 parts of 2-a1nino-3.5-dimethyl-l-(4'-phenylphenoxy)-benzene or 141.2 parts of 2 amino 3.5dimethyl 1 (4 phenylsulphonylphenoxy) benzene or 97.2 parts of 2 amino3.4'.5- trimethyl 1 thiophenoxybenzene or 105.4 parts of 2- amino 3.5dimethyl l (4 chlorothiophenoxy)- benzene are used then similar bluedyestuffs which draw Well from a neutral bath are obtained, the wooldyeings of which have good fastness to washing, milling and light.

Example 10 A mixture of 12 parts of 1.4-dihydroxyanthraquinone, 12.1parts of leuco quinizarin, 9 parts of metaboric acid and 82.2 parts of 3amino 2.4 dimethyl l phenoxybenzene is melted with 25 parts of glacialacetic acid and 3.5 parts of 30% hydrochloric acid, and the thin liquidmelt is kept at 110-115 for 30 hours in a nitrogen atmosphere. Afterthis time, the condensation product has precipitated as a thickcrystalline mass. Some of it is in the leuco form. To convert into thedye base, 200 parts of sec. butyl alcohol and 4.2 parts of 30% causticsoda lye are added at 90 and air is introduced into the reaction mixturefor some hours at 90-100 until there is no more leuco compound present.The reaction mixture is cooled to room temperature and the crystalline,bronze gleaming 1.4 bis (3' phenoxy 2.6' dimethylanilido)-anthraquinoneof the formula:

NHQO I is drawn off under suction. The dye base is obtained in a pureform by washing the filter residue with hot methyl alcohol. The drieddye base is then sulphonated by the usual methods, for example bystirring 10 parts in 100 parts of concentrated sulphuric acid at 1520until a sample dissolves completely in a lot of hot water. The dyestuffis precipitated by dilution with water, drawn off under suction andconverted in the usual way into the sodium salt, isolated and dried. Itis a dark blue powder which dissolves in water and in concentratedsulphuric acid with a blue colour and dyes wool, silk and polyamidefibres from a neutral bath in the presence of ammonium sulphate in veryfast reddish blue shades.

If instead of 82.2 parts of 3-amino2.4dimethyl-1- phenoxybenzene, 90.8parts of 3-amino-2.4.4-trimethyll-phenoxybenzene are condensed, then asimilar dyestufi which draws well from a neutral bath is obtained.

Example 11 100 parts of wool flannel are entered at 40-45 into a dyebathconsisting of 1 part of the dyestufi according to example 2, 3 parts ofammonium sulphate or parts of ammonium acetate and parts of Glauberssalt in 3000 parts of water. The bath is gradually brought to the boilwithin 45 minutes, kept at the light boil for half an hour and then thedyed goods are rinsed. A very level reddish blue wool dyeing is obtainedwhich has verygood fastness to milling, sea water and light.

Similar dyeings are obtained if dyestufis according to the otherexamples are used under the same conditions.

What we claim is:

1. An acid dyestufi of the anthraquinone series having the generalformula:

0 NH- an X2 Y1 L9 ]so,rr Z rcon;

wherein oneof X and X represents a member selected from the groupconsisting of phenyloxy, phenylthio and naphthyloxy radicals and theother one represents a member selected from the group consisting ofhydrogen and the methyl group, Y and Y each represent a member selectedfrom the group consisting of hydrogen and halogen, and wherein X isalways different from hydrogen. v

2. An acid dyestuff of the anthraquinone series having the generalformula:

L i1 Tsom wherein X represents an aryl ether substituent selected fromthe group consisting of phenyloxy, phenylthio and naphthyloxy radicals,Y and Y each represent a member selected from the group consisting ofhydrogen and halogen.

4. An acid dyestuff of the anthraquinone series having the formula:

;5. An acid dyestuif of the anthraquinone series having the formula:

I CH

the formula:

6. An acid dyestuff of the anthraquinone series having the formula 15 8.An acid dyestuff of the anthraquinone series having References Cited inthe file of this patent UNITED STATES PATENTS Mettler Q May 16, 1939Allmen et a1. Aug. 26, 1941 Hindermann et a1 Aug.-28, 1956

1. AN ACID DYESTUFF OF THE ANTRAQUINONE SERIES HAVING THE GENERALFORMULA: